CN1297570C - Method for hydrogenation of polymers in dispersed medium - Google Patents
Method for hydrogenation of polymers in dispersed medium Download PDFInfo
- Publication number
- CN1297570C CN1297570C CNB028291204A CN02829120A CN1297570C CN 1297570 C CN1297570 C CN 1297570C CN B028291204 A CNB028291204 A CN B028291204A CN 02829120 A CN02829120 A CN 02829120A CN 1297570 C CN1297570 C CN 1297570C
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- Prior art keywords
- desired method
- reductive agent
- oxygenant
- hydrazine
- carboxylic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/02—Hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a method for hydrogenating unsaturated polymers in a dispersive medium based on an oxidation-reduction system. The oxidation-reduction system comprises hydrazine and an oxidizing agent, such as peroxide, and the oxidation-reduction system comprises or does not comprise carboxylic acid. The hydrogenation rate can reach 100% in certain conditions.
Description
The present invention relates to the method for hydrogenation of unsaturated polymer, specifically relate to unsaturated polymer and in dispersion medium, carry out the hydrogenant method with oxidation/reduction system.This redox system comprises hydrazine or its a kind of derivative, oxygenant and the optional carboxylic acid that contains or do not contain.
As everyone knows, the structures shape of polymkeric substance its physicochemical property.For example, the polymkeric substance (below be called unsaturated polymer) that comprises one or more olefinic double bonds is a softish and resilient.For this reason, they have a lot of purposes.
But because olefinic double bond is to the oxidizing reaction sensitivity, this makes unsaturated polymer to heat and/or ultraviolet ageing instability, so their application is restricted.
Reduce after the degree of unsaturation of unsaturated polymer, they have reduced for the susceptibility of oxidizing reaction.The reduction of degree of unsaturation is carried out with hydrogenation usually.
Use for some, must between polymer elasticity and its susceptibility, find a kind of balance oxidation.Here it is control hydrogenation technology advantage.
Method for hydrogenation and used reaction are known and it existing are comprehensively described.Some existing index record.
WO 00/009576 discloses and has used a kind of system that comprises hydrazine, oxygenant and contain the catalyzer of the periodic table of elements the 13rd family's element to carry out the hydrogenation of unsaturated polymer (for example elastomerics of representing with NBR based on nitrile and divinyl).
US 5302696 discloses a kind of use hydrazine, oxygenant and molysite or mantoquita makes latex carry out the hydrogenant method.Be used for NBR latex.
WO 91/06579 discloses from hydrazine and oxygenant and has had the little method of solidifying rubber of hydrogenant NBR latex preparation saturation ratio down.
US 5902889 discloses in the presence of oxygenant and metal-salt and has made the unsaturated fatty acid salt aqueous solution carry out the hydrogenant method with hydrazine.
US 5442009 disclose a kind of in the presence of oxygenant, hydrazine and metal-salt by latex hydrogenation is prepared the method that hydrogenant " is done " rubber.Be applied to NBR latex.
US 5424356 discloses in the presence of hydrazine and metal-salt by prepare the method for hydrorubber with oxidizer treatment latex (NBR).
WO 92/17512 discloses in the presence of oxygenant, hydrazine and metal-salt unsaturated latex hydrogenation.Mentioned latex is: (I) divinyl, (II) vinyl cyanide, isoprene or divinyl and/or (III) styrol copolymer.
Two keys that US 4452950 discloses in the presence of hydrazine, oxygenant and metal-salt the unsaturated polymer of latex form carry out the hydrogenant method.
From the above as seen, all these documents all disclose the method for hydrogenation that uses metal-salt.
Applicant's company has found and has developed a kind of method for hydrogenation easy to implement, and this method is inexpensive and do not need to use metal-salt.
According to the present invention and the method for hydrogenation that constitutes the unsaturated polymer of the present invention's first theme be based on a kind of the employing hydrazine, oxygenant and optional containing/or do not contain the oxidation/reduction system of carboxylic acid.
Use method of the present invention, unsaturated polymer must be dispersed in the water-bearing media.Therefore this method is easy for the stabilized latex of unsaturated polymer.But be not restricted to this class latex.This method also can be used for all unsaturated polymers, and is no matter it is liquid or solid-state, simple or in solution, as long as they can be scattered in the water under mechanical stirring.
Method of the present invention may further comprise the steps: under simple and mechanical stirring unsaturated polymer is scattered in the water, add subsequently hydrazine all or part of and optional add or do not add carboxylic acid, reaction medium is heated to temperature desired, by moving continuously simultaneously the hydrazine and the oxygenant of remainder is added then.
If unsaturated polymer is the latex state, then various additives are directly added so far among the latex, if unsaturated polymer is liquid or pulverulence, then its is disperseed among the water inlet by simple and mechanical stirring.On the other hand, if the polymkeric substance that is hydrogenated is a solid, then among the first step is dissolved in it minimum organic solvent, subsequently it is disperseed.
If unsaturated polymer is water-soluble, then hydrogenation is directly carried out in the aqueous solution.
As the unsaturated polymer that can carry out method for hydrogenation of the present invention, can mention:
The sense of-diene or non-functional oligomers, for example divinyl, isoprene, 2, the oligopolymer of 3-dimethylbutadiene or chloroprene, and their multipolymer or they and one or more other vinyl monomers each other, as alkyl ester, vinyl ether, vinyl acetate, the halogenated olefine (VF of derivative, vinyl cyanide, propylene or the methacrylic acid of vinylbenzene or its replacement
2, VCM or the like) and the multipolymer of allyl ethers.
These oligopolymer can make with following any known polymerization process: radical polymerization method, anionic polymerization, Z-N method, metathesis polymerization method or the like.
These oligopolymer can be functionalized on the end of the chain or chain, the polyhutadiene of for example the hydroxyl telechelic, amino telechelic or carboxyl telechelic, the maleation polyhutadiene, the carboxyl telechelic multipolymer of divinyl and vinyl cyanide, divinyl and cinnamic carboxyl telechelic multipolymer etc.
-be dispersed in the sense in the water or the solid-state unsaturated polymer of non-functional emulsoid and powder dispersion state, comprise dienes, for example divinyl, isoprene, 2,3-dimethylbutadiene or chloroprene, and their multipolymer or they and one or more other vinyl monomers each other, as derivative, vinyl cyanide, acrylic or methacrylic acid alkyl ester, vinyl ether, vinyl acetate, the halogenated olefine (VF of vinylbenzene or its replacement
2, VCM or the like) and the multipolymer of allyl ethers.
-be dissolved in the solid-state unsaturated polymer in organic dissolution solvent, its solution can be dispersed in the water, these polymkeric substance comprise dienes, for example divinyl, isoprene, 2,3-dimethylbutadiene or chloroprene, and their multipolymers each other or they and other's vinyl monomer, as derivative, vinyl cyanide, acrylic or methacrylic acid alkyl ester, vinyl ether, vinyl acetate, the halogenated olefine (VF of vinylbenzene or its replacement
2, VCM or the like) and the multipolymer of allyl ethers.
These oligopolymer can make with following any known polymerization process: radical polymerization method, anionic polymerization, Z-N method or metathesis polymerization method.
The solvent that can make them become dispersion liquid in water can be aliphatic hydrocrbon, aromatic hydrocarbon, cyclic ethers or acyclic ether, alcohol or the like.Its example can be mentioned hexane, heptane, benzene, toluene, ethylbenzene, ether, butyl ether, tetrahydrofuran (THF), methyl alcohol, ethanol, Virahol or the like.
-contain and be not the undersaturated solid polymer or the dissolved polymers that obtain from diene monomers for example to contain the polymkeric substance that brings the unsaturated chain defective because of the preparation method.That can point out has PVC, PMMA or the like, and no matter what (mass polymerization, suspension polymerization or letex polymerization) is its synthetic method be.
Reductive agent is a kind of of hydrazine or derivatives thereof, for example list of hydrazine hydrate, hydrazine or two hydrohalogens, or the carboxylate salt of hydrazine.
Oxygenant can be oxygen or superoxide R-OO-R ', and R and R ' can be hydrogen or saturated straight chain, ring-type or branched-alkyl in the formula.The example can be mentioned hydrogen peroxide, hydrogen peroxide butyl, dicumyl peroxide or the like.
Be selected from aliphatic carboxylic acid or aromatic carboxylic acid as the carboxylic acid of catalyzer, for example formic acid, acetate, phenylformic acid, stearic acid or the like, and their alkaloid salt.
This method for making comprises and generates the active body imide on the spot, and this imide is by the right cis addition of proton and emits nitrogen and make the two key hydrogenant selective hydrogenant agents of C-C.
Hydrogenation carries out in the reactor that humidity control system, effective agitator, charging pump, the valve of removing the gaseous state ejecta and the optional condenser that is with or without are installed.
If agitator can make reactant fully exchange, then be considered to effective between water and organic phase.Viscosity and their dispersing propertys in water of product depended in the selection of agitator, can perhaps select between their combination at anchor stirrer, impeller-type stirrer, turbine mixing tank or spiral turner, and reactor also can be installed baffle plate.
Existing or not existing under solvent and water (is under the situation of latex or dispersion liquid state at polymkeric substance) or the anhydrous situation, the polymerization that is hydrogenated is added in this reactor.A part of reductive agent that hydrogenation is required adds to be had in the reactor of carboxylic acid, and remaining reductive agent during reaction adds continuously with a suitable pump, meanwhile adds whole oxygenants with another pump.Hydrogenation carries out under normal atmosphere or controlled vacuum under 0～100 ℃, preferred 50～100 ℃.The advantage of reacting under controlled vacuum is that it uses condenser to improve the heat-exchange capacity of reactor.
The progress of reaction can be monitored by observing liberated heat, or the nitrogen amount monitoring by generating in the observing response process.
The amount of the required reductive agent of hydrogenation is to limit with the degree of unsaturation that is hydrogenated.Should select reductive agent for use, preferably between 1 and 2, be more preferably between 1.2 and 2 above stoichiometric quantity.When beginning reaction join reductive agent quantity in the reactor be total quantity 0 to 100% between, between preferred 10 to 70%, remaining reductive agent between 0.1 and 5 hour, preferably adds in the time between 0.5 and 2 hour in reaction process.
Selection as the carboxylic acid amount of catalyzer is, in the mole number of reductive agent, is chosen as between 0 and 20 mole of %, preferably between 0 and 10 mole of %, particularly is lower than 5 moles of %.Whole catalyzer can be mixed with reductive agent before it is added into reactor or in the reinforced process.If polymkeric substance itself has carboxylic acid or carboxylate salt functional group, then can there be carboxylic acid, this does not leave scope of the present invention.
The amount of the required oxygenant of hydrogenation limits with reduction dosage.Be preferably between 1 and 2 with the excessive mol ratio of stoichiometric quantity, more preferably between 1 and 1.5.Excessive the making of this stoichiometric quantity can guarantee that when reaction end reductive agent is consumed.In the whole process of reaction, add oxygenant continuously so that control reaction temperature; The flow velocity of reagent must make selected temperature of reaction can keep constant.Therefore the full time of reaction depends on the heat-exchange capacity of reactor.
When the end of reaction, can under temperature of reaction, carry out after fixing 0 to 90 minute, more preferably 15 to 60 minutes.
When finishing, reaction according to the hydropolymer that is obtained with wish the different of the state of polymer that reclaims,, then reaction mixture can be cooled off simply if wish form recovery hydropolymer with dispersion liquid; And if wish that with powder type recovery hydropolymer the non-solvent that then adds hydropolymer makes its precipitation, or it is delivered in another reactor that non-solvent is housed.In this case, the hydrogenant polymkeric substance is washed under the condition that is suitable for its structure and non-solvent character, filtration and dried recovered.
Compare with the hydrogenation that carries out in the presence of transition metal and hydrogen of routine, method of the present invention shows following advantage:
carries out hydrogenation in dispersion medium, reduced the usage quantity of organic solvent.
carries out hydrogenation under normal atmosphere or decompression, simplified industrial equipments.
carries out the final processing of product with precipitation, filtration, washing and fan-drying, has simplified the industrial equipments of downstream part.
by product nonstaining property, for example water and nitrogen.
The selective hydration of the two keys of C-C makes the polymkeric substance with complex construction can carry out hydrogenation.
The following example is explained the present invention, but does not limit the scope of the invention.
Embodiment
1. the hydrogenation of hydroxylated polybutadiene
1.1 according to embodiments of the invention
In a glass jacket reactor, Atofina is carried out hydrogenation with the hydroxylated polybutadiene (HTPB) that trade mark Poly Bd R-45HT sells, this reactor is equipped with the agitator of turbine mixing type or the hybrid agitator of anchor stirrer and paddle wheel, baffle plate is housed, reflux exchanger is housed and two pumps can controlling reductive agent and oxidizer flow rate are housed.With the 100g molecular-weight average is 2900 HTPB, the 50g deionized water, and the hydrazine hydrate in water of 74g 64% weight, and the pure acetate of the 9g of equivalent is sent in the reactor.The hydrazine hydrate in water of 74g 64% weight and the hydrogen peroxide in water of 282g 50% weight are sent into respectively in the feeder hopper of two pumps.
Under 300 rev/mins stirring, reaction mixture is heated to 65 ℃.Then flow, the hydrogen peroxide of hydrazine hydrate with 74g/h begun to send into simultaneously with the flow of 47g/h.Temperature is arranged on 75 ℃, and controls with jacket temperature.
After hydrogen peroxide adds, spend 6 hours and make reaction medium in 45 minutes, rise to 80 ℃.By adding 500ml deionized water and reduction temperature is set then, makes medium be cooled to envrionment temperature.
Hydrogenant HTPB forms white powder subsequently in aqueous dispersions, it filter, wash with water, fan-drying and dry in fluidized-bed then.
The proton N MR of employing in the deuterate chloroform analyzes that can quantitative assay to go out hydrogenation degree be 99%.NMR also analyzes and confirms that alcohol functional group has remained in hydrogenated products.
1.2 Comparative Examples 1
Identical be reflected at not have acetate but exist under the condition of 0.1g copper sulfate carry out, obtain being with orange-yellow hydrogenation HTPB, the hydrogenation degree of measuring with proton N MR is 30%.
1.3 Comparative Examples 2
Identical being reflected under the condition that does not have acetate and copper sulfate carried out, and obtains hydrogenation HTPB, and the hydrogenation degree of measuring with proton N MR is 25%.
2. based on the hydrogenation of the polyurethane aqueous dispersion of hydroxyl telechelic polyhutadiene.
As described in the French Patent 98/03793 of Atofina, preparation is based on the urethane aqueous dispersion of hydroxyl telechelic polyhutadiene.The solids content of the dispersion liquid that so makes is 30%, and particle diameter is 100nm, and polybutadiene content is 22% weight.
This dispersion liquid of 250ml is sent in the reactor identical with embodiment 1, and this reactor is equipped with anchor stirrer and paddle wheel, contains the hydrazine hydrate of 40.5g 64% in water.Because this dispersion liquid contains for stablizing the carboxylate radical of usefulness, so do not add acetate.Hydrazine hydrate and 155g 50% the hydrogen peroxide in water of 40.5g 64% weight in water joined respectively in the feed hopper of two pumps.
Under 200 rev/mins stirring, reaction mixture is heated to 65 ℃.Then with the flow of hydrazine hydrate with 40g/h.Hydrogen peroxide begins to send into simultaneously with the flow of 38.75g/h.Temperature is arranged on 75 ℃, and controls with jacket temperature.
After hydrogen peroxide adds, spend 4 hours and make reaction medium in 45 minutes, rise to 80 ℃, by reduction temperature is set then and makes medium be cooled to envrionment temperature.
Obtained solids content and be 17.5% and particle diameter be the stabilized polyurethane dispersion liquid of 100nm based on hydrogenation hydroxyl telechelic polyhutadiene.The hydrogenation structure that confirms product with infrared analysis on the film and solid NMR is greater than 99%, and this film is dry and make with dispersion liquid.
3. the hydrogenation of phenylethylene/butadiene/methyl methacrylate segmented copolymer
EP 524054 or EP 749987 according to Atofina prepare the block terpolymer that contains 38% weight styrene, 38% weight butadiene and 24% weight methacrylic acid methyl esters.
With this terpolymer of 60g, 300g ethylbenzene and 30g deionized water are sent in the reactor that the turbine agitator is installed identical with embodiment 1, are placed with the hydrazine hydrate of 17g 64% in water and the pure acetate of 2g of equivalent in the reactor.17g 64% weight hydrazine hydrate and the hydrogen peroxide of 64g 50% in water are sent into respectively in the feeder hopper of two pumps.
Under 250 rev/mins stirring, reaction mixture is heated to 65 ℃.Then with the flow of hydrazine hydrate with 17g/h.Hydrogen peroxide begins to send into simultaneously with the flow of 16g/h.Temperature is arranged on 75 ℃, and controls with jacket temperature.
After hydrogen peroxide adds, spend 4 hours and make reaction medium in 45 minutes, rise to 80 ℃, temperature is set and adds 400ml technical grade ethanol by reduction then, make medium be cooled to envrionment temperature.
The hydrogenant terpolymer formation white powder in aqueous dispersions subsequently, it filter, wash with water, fan-drying is dry in a vacuum then.
It is 99.6% that proton N MR in the deuterate chloroform analyzes the hydrogenation degree that quantitatively records polyhutadiene embedding hall, and NMR analyzes also and confirms that vinylbenzene and methyl methacrylate block have remained.
4. the hydrogenation of styrene-butadiene-styrene block copolymer
60g Finaprene 602,300g ethylbenzene and 30g deionized water are sent in the reactor that the turbine mixing machine is housed identical with embodiment 1, be placed with the hydrazine hydrate of 27g 64% in water and the pure acetate of 3g of equivalent in the reactor.Hydrazine hydrate and 101g 50% the hydrogen peroxide in water of 26g 64% weight in water sent into respectively in the feeder hopper of two pumps.
Under 250 rev/mins stirring, reaction mixture is heated to 65 ℃.Then with the flow of hydrazine hydrate with 26g/h.Hydrogen peroxide begins to send into simultaneously with the flow of 25g/h.Temperature is arranged on 75 ℃, and controls with jacket temperature.
After hydrogen peroxide adds, spend 4 hours and make reaction medium in 45 minutes, rise to 80 ℃, by reduction temperature is set then and makes medium be cooled to envrionment temperature.
By will be hydrogenant Finaprene 602 send in 1 liter of technical grade ethanol and it settled out with the long filament shape, precipitation fan-drying drying under vacuum then.
It is 95% that proton N MR in the deuterate chloroform analyzes the hydrogenation degree of quantitatively measuring polybutadiene block.NMR analyzes and also confirms that styrene block has remained.
Claims (12)
1. the unsaturated polymer that will contain olefinic double bond carries out the hydrogenant method, this method use reductive agent, oxygenant and optional with or carry out without carboxylic acid, wherein hydrogenation carries out in stable aqueous dispersion, or carries out in unstable aqueous dispersion; The mol ratio of oxygenant/reductive agent is between 1 and 2; Reductive agent is selected from single or two hydrohalogens of hydrazine, hydrazine hydrate, hydrazine, the perhaps carboxylate salt of hydrazine; Oxygenant is selected from oxygen or superoxide R-OO-R ', and R and R ' are hydrogen or saturated straight chain, ring-type or branched-alkyl in the formula.
2. as desired method in the claim 1, it is characterized in that stable aqueous dispersion is a latex, and unstable aqueous dispersion is a mechanical dispersion liquid.
3. as desired method in claim 1 or 2, it is characterized in that:
The mol ratio of the unsaturates of reductive agent/be hydrogenated is between 1 and 2;
The mol ratio of oxygenant/reductive agent is between 1 and 1.5;
Acid amount in reductive agent between 0 and 20 mole of %.
4. as desired method in the claim 3, it is characterized in that: the mol ratio of the unsaturates of reductive agent/be hydrogenated is between 1.2 and 2.
5. the desired method of arbitrary as described above claim is characterized in that being reflected under the temperature between 0 to 100 ℃ and carries out.
6. desired method in the claim 5 as described above is characterized in that being reflected under the temperature between 50 to 100 ℃ and carries out.
7. as desired method in the claim 1, it is characterized in that reductive agent is a hydrazine.
8. the desired method of arbitrary as described above claim is characterized in that oxygenant is selected from hydrogen peroxide, hydrogen peroxide butyl, dicumyl peroxide.
9. as desired method in the claim 8, it is characterized in that oxygenant is a hydrogen peroxide.
10. the desired method of arbitrary as described above claim is characterized in that carboxylic acid is selected from aliphatic carboxylic acid or aromatic carboxylic acid.
11. the desired method of claim 10 is characterized in that carboxylic acid is selected from formic acid, acetate, phenylformic acid, stearic acid or their alkaloid salt as described above.
12., it is characterized in that this carboxylic acid is an acetate as desired method in the claim 11.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/FR2002/001261 WO2003093326A1 (en) | 2002-04-11 | 2002-04-11 | Method for hydrogenation of polymers in dispersed medium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1628130A CN1628130A (en) | 2005-06-15 |
| CN1297570C true CN1297570C (en) | 2007-01-31 |
Family
ID=29286322
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028291204A Expired - Fee Related CN1297570C (en) | 2002-04-11 | 2002-04-11 | Method for hydrogenation of polymers in dispersed medium |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US7148292B2 (en) |
| EP (1) | EP1492823B1 (en) |
| JP (1) | JP4456478B2 (en) |
| KR (1) | KR20040101442A (en) |
| CN (1) | CN1297570C (en) |
| AT (1) | ATE387463T1 (en) |
| AU (1) | AU2002304522A1 (en) |
| CA (1) | CA2482355A1 (en) |
| DE (1) | DE60225346T2 (en) |
| ES (1) | ES2301644T3 (en) |
| WO (1) | WO2003093326A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8207386B2 (en) * | 2003-12-08 | 2012-06-26 | Nitta Corporation | Rubber-like articles and rubber-like material-containing articles |
| CA2501199A1 (en) * | 2005-03-18 | 2006-09-18 | Lanxess Inc. | Organic solvent-free hydrogenation of diene-based polymers |
| KR101452020B1 (en) * | 2010-09-03 | 2014-10-22 | 주식회사 엘지화학 | Thermoplastic resin composition with excellent weatherability and a method for preparing thereof |
| KR101391016B1 (en) * | 2012-12-14 | 2014-04-30 | 주식회사 엘지화학 | Thermoplastic resin compositions having improved weathering durability and method for perparing them |
| CN105622784B (en) * | 2016-02-01 | 2018-02-16 | 浙江大学 | Hydroxy functionalized polyethylene and preparation method thereof |
| FR3078706B1 (en) | 2018-03-07 | 2020-12-18 | Total Marketing Services | THERMOASSOCIATIVE AND EXCHANGEABLE COPOLYMERS, COMPOSITION INCLUDING THEM |
| FR3078710B1 (en) | 2018-03-07 | 2020-10-30 | Total Marketing Services | COMPOSITION INCLUDING THERMOASSOCIATIVE AND EXCHANGEABLE COPOLYMERS |
| WO2023145960A1 (en) | 2022-01-31 | 2023-08-03 | 株式会社ダイセル | Thermosetting resin composition, resin composition for printed wiring board, and resin composition for printed wiring board substrate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5057601A (en) * | 1989-11-06 | 1991-10-15 | Olin Corporation | Process for producing a gel-free coagulated rubber with low ethylenic unsaturation |
| US5302696A (en) * | 1989-05-16 | 1994-04-12 | Olin Corporation | Process for minimizing residual free hydrazine in polymer latices |
| WO2000009576A1 (en) * | 1998-08-11 | 2000-02-24 | Dsm N.V. | Process for hydrogenation of carbon-carbon double bonds of an unsaturated polymer |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4452950A (en) * | 1983-02-22 | 1984-06-05 | The Goodyear Tire & Rubber Company | Process for hydrogenation of carbon-carbon double bonds in an unsaturated polymer in latex form |
| US5221714A (en) | 1991-04-04 | 1993-06-22 | The Goodyear Tire & Rubber Company | Blend of rubber latices containing a hydrogenated rubber latex |
| FR2679237B1 (en) | 1991-07-19 | 1994-07-22 | Atochem | PRIMING SYSTEM FOR THE ANIONIC POLYMERIZATION OF (METH) ACRYLIC MONOMERS. |
| US5258467A (en) * | 1992-09-02 | 1993-11-02 | Polysar Rubber Corporation | Catalytic solution hydrogenation of nitrile rubber |
| US5424356A (en) * | 1994-03-21 | 1995-06-13 | The Goodyear Tire & Rubber Company | Process for the preparation of hydrogenated rubber |
| FR2735480B1 (en) | 1995-06-15 | 1997-07-18 | Atochem Elf Sa | CONTINUOUS ANIONIC POLYMERIZATION PROCESS OF AT LEAST ONE (METH) ACRYLIC MONOMER FOR THE OBTAINING OF POLYMERS WITH A HIGH SOLID RATE |
| US5902889A (en) | 1997-09-18 | 1999-05-11 | The Goodyear Tire & Rubber Company | Process for hydrogenation of carbon-carbon double bonds of a water-soluble olefinically unsaturated carboxylic acid salt |
| FR2776662B1 (en) | 1998-03-25 | 2000-05-05 | Atochem Elf Sa | AQUEOUS POLYURETHANE DISPERSIONS AND THEIR PREPARATION PROCESS |
-
2002
- 2002-04-11 ES ES02732802T patent/ES2301644T3/en not_active Expired - Lifetime
- 2002-04-11 CN CNB028291204A patent/CN1297570C/en not_active Expired - Fee Related
- 2002-04-11 EP EP02732802A patent/EP1492823B1/en not_active Expired - Lifetime
- 2002-04-11 WO PCT/FR2002/001261 patent/WO2003093326A1/en active IP Right Grant
- 2002-04-11 US US10/510,830 patent/US7148292B2/en not_active Expired - Fee Related
- 2002-04-11 KR KR10-2004-7016229A patent/KR20040101442A/en not_active Application Discontinuation
- 2002-04-11 DE DE60225346T patent/DE60225346T2/en not_active Expired - Lifetime
- 2002-04-11 AU AU2002304522A patent/AU2002304522A1/en not_active Abandoned
- 2002-04-11 JP JP2004501465A patent/JP4456478B2/en not_active Expired - Fee Related
- 2002-04-11 AT AT02732802T patent/ATE387463T1/en not_active IP Right Cessation
- 2002-04-11 CA CA002482355A patent/CA2482355A1/en not_active Abandoned
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5302696A (en) * | 1989-05-16 | 1994-04-12 | Olin Corporation | Process for minimizing residual free hydrazine in polymer latices |
| US5057601A (en) * | 1989-11-06 | 1991-10-15 | Olin Corporation | Process for producing a gel-free coagulated rubber with low ethylenic unsaturation |
| WO2000009576A1 (en) * | 1998-08-11 | 2000-02-24 | Dsm N.V. | Process for hydrogenation of carbon-carbon double bonds of an unsaturated polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1628130A (en) | 2005-06-15 |
| ES2301644T3 (en) | 2008-07-01 |
| KR20040101442A (en) | 2004-12-02 |
| AU2002304522A1 (en) | 2003-11-17 |
| EP1492823B1 (en) | 2008-02-27 |
| ATE387463T1 (en) | 2008-03-15 |
| US7148292B2 (en) | 2006-12-12 |
| JP2005522577A (en) | 2005-07-28 |
| US20050261445A1 (en) | 2005-11-24 |
| EP1492823A1 (en) | 2005-01-05 |
| CA2482355A1 (en) | 2003-11-13 |
| JP4456478B2 (en) | 2010-04-28 |
| WO2003093326A1 (en) | 2003-11-13 |
| DE60225346D1 (en) | 2008-04-10 |
| DE60225346T2 (en) | 2009-02-19 |
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